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A kind of bichiral central cyclopropylsilane compound and its preparation method and application

A technology of cyclopropylsilane and compound, which is applied in the field of chiral center cyclopropylsilane compound and its preparation, can solve the problems of restricted structure diversification and the like, achieves strong substrate universality, novel synthesis method and mild reaction conditions Effect

Active Publication Date: 2022-03-08
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, such methods are very limited. For each cyclopropane, different alkene or carbene precursors are required, which greatly limits the structural diversification.

Method used

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  • A kind of bichiral central cyclopropylsilane compound and its preparation method and application
  • A kind of bichiral central cyclopropylsilane compound and its preparation method and application
  • A kind of bichiral central cyclopropylsilane compound and its preparation method and application

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Under nitrogen atmosphere, add phosphine ligand L2:(R)-DTBM-SegPhos (8.5mg, 0.0072mmol) to Schlenk reaction tube, metal catalyst [Rh(cod) 2 ] BF 4 (2.5mg, 0.006mmol) and additive tetrakis(3,5-bis(trifluoromethyl)phenyl)sodium borate (5.3mg, 0.006mmol), then add 2.0mL n-hexane solvent, and pre-stir at 30°C for 20min Finally, add cyclopropene compound 1a (0.20mmol), stir for 15min, then add diphenylsilane (0.26mmol), continue to stir and react at 30°C for 20h, after the reaction is monitored by TLC, filter, extract, concentrate the filtrate, and pass through silica gel Purified by column chromatography, 50 mg of product 1c was obtained as a light yellow oily liquid with a yield of 70%, 92% ee, 93:7dr.

[0046]

[0047] The physicochemical index of this product: 1 H NMR (400MHz, CDCl 3 )δ7.64–7.57(m,2H),7.53(dd,J=7.1,2.0Hz,2H),7.28(dd,J=6.5,2.6Hz,4H),7.27–7.23(m,4H),7.19 (t,J=7.3Hz,2H),7.17–7.10(m,1H),4.90(d,J=4.4Hz,1H),3.22(s,3H),1.76(dd,J=8.6,3.4Hz, 1H), 1.56(dd,...

Embodiment 2

[0049] Under nitrogen atmosphere, add phosphine ligand L2:(R)-DTBM-SegPhos (8.5mg, 0.0072mmol) to Schlenk reaction tube, metal catalyst [Rh(cod) 2 ] BF 4 (2.5mg, 0.006mmol) and additive tetrakis(3,5-bis(trifluoromethyl)phenyl)sodium borate (5.3mg, 0.006mmol), then add 2.0mL n-hexane solvent, and pre-stir at 30°C for 40min Finally, add cyclopropene compound 1a (0.20mmol), stir for 15min, then add diphenylsilane (0.26mmol), continue to stir and react at 30°C for 20h, after the reaction is monitored by TLC, filter, extract, concentrate the filtrate, and pass through silica gel Purified by column chromatography, 60 mg of product 1c was obtained as light yellow oily liquid with a yield of 84%, 98% ee, 97:3dr.

[0050]

[0051] The physicochemical index of this product: 1 H NMR (400MHz, CDCl 3 )δ7.64–7.57(m,2H),7.53(dd,J=7.1,2.0Hz,2H),7.28(dd,J=6.5,2.6Hz,4H),7.27–7.23(m,4H),7.19 (t,J=7.3Hz,2H),7.17–7.10(m,1H),4.90(d,J=4.4Hz,1H),3.22(s,3H),1.76(dd,J=8.6,3.4Hz, 1H), 1.56(dd, J...

Embodiment 3

[0053] Under nitrogen atmosphere, add phosphine ligand L2:(R)-DTBM-SegPhos (8.5mg, 0.0072mmol) to Schlenk reaction tube, metal catalyst [Rh(cod) 2 ] BF 4 (2.5mg, 0.006mmol) and additive tetrakis(3,5-bis(trifluoromethyl)phenyl)sodium borate (5.3mg, 0.006mmol), then add 2.0mL n-hexane solvent, and pre-stir at 30°C for 60min Finally, add cyclopropene compound 1a (0.20mmol), stir for 15min, then add diphenylsilane (0.26mmol), continue to stir and react at 30°C for 20h, after the reaction is monitored by TLC, filter, extract, concentrate the filtrate, and pass through silica gel Purified by column chromatography, 50 mg of product 1c was obtained as a light yellow oily liquid with a yield of 70%, 90% ee, 90:10dr.

[0054]

[0055] The physicochemical index of this product: 1 H NMR (400MHz, CDCl 3 )δ7.64–7.57(m,2H),7.53(dd,J=7.1,2.0Hz,2H),7.28(dd,J=6.5,2.6Hz,4H),7.27–7.23(m,4H),7.19 (t,J=7.3Hz,2H),7.17–7.10(m,1H),4.90(d,J=4.4Hz,1H),3.22(s,3H),1.76(dd,J=8.6,3.4Hz, 1H), 1.56(dd...

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Abstract

The invention relates to the field of chiral organosilanes, and specifically discloses a bichiral central cyclopropylsilane compound shown in formula (I) and a preparation method thereof, comprising: combining cyclopropene shown in formula (II) with diphenyl Cyclopropylsilane compounds with high yield and high enantioselectivity were efficiently synthesized by asymmetric hydrosilylation reaction of cyclopropylsilane. Compared with the traditional [2+1] cycloaddition and 1,3-cyclization substituted cyclopropylamino reactions, it is a more direct and effective method for the synthesis of cycloalkane compounds, and can obtain a variety of different compounds that cannot be prepared by traditional methods. Cyclopropylsilane compounds with substituents are widely used in the fields of materials chemistry and medicinal chemistry.

Description

technical field [0001] The invention relates to the field of chiral organosilanes, in particular to a bichiral central cyclopropylsilane compound and its preparation method and application. Background technique [0002] Chiral organosilanes are gradually playing an important role in siliceous substitution in organic synthesis, materials science and medicinal chemistry, among which chiral silicon-containing organic compounds are very useful synthetic blocks in organic chemistry; silane-substituted compounds are due to their Low toxicity and favorable metabolic characteristics have attracted increasing attention in medicinal chemistry; chiral catalysts containing silicon atoms are also widely used in asymmetric organocatalysis. Silicon-based chiral compounds are important components for selective carbon-carbon bond formation, and the asymmetric hydrosilylation of alkenes provides a direct route to construct chiral organosilanes. [0003] 3,3-Disubstituted cyclopropylsilanes a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F7/08C07F7/12C07D401/04C07C235/82C07C61/37C07C57/50
CPCC07F7/0896C07F7/122C07D401/04C07C235/82C07C61/37C07C57/50C07C2601/02C07C2602/10C07C2602/24C07B2200/07
Inventor 徐利文赵志远杨雪敏郭彬徐征曹建尹官武郑战江叶飞杨科芳崔玉明
Owner HANGZHOU NORMAL UNIVERSITY
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